Atomically engineering metal vacancies in monolayer transition metal dichalcogenides

Scanning probe microscopy and scanning transmission electron microscopy (STEM) are powerful tools to trigger atomic-scale motions, pattern atomic defects and lead to anomalous quantum phenomena in functional materials. However, these techniques have primarily manipulated surface atoms or atoms located at the beam exit plane, leaving buried atoms, which govern exotic quantum phenomena, largely unaffected. Here we propose an electron-beam-triggered chemical etching approach to engineer shielded metal atoms sandwiched between chalcogen layers in monolayer transition metal dichalcogenide (TMDC). Various metal vacancies \(({{{\mathrm{V}}}}_{{{\rm{MX}}}_{{n}}},\,{n}=0{-}6)\) $\left({\mathrm{V}}_{{\mathrm{MX}}_n},n=0-6\right)$ have been fabricated via atomically focused electron beam in STEM. The parent TMDC surface was modified with surfactants, facilitating the ejection of sandwiched metal vacancies via charge transfer effect. In situ sequential STEM imaging corroborated that a combined chemical-induced knock-on effect and chalcogen vacancy-assisted metal diffusion process result in atom-by-atom vacancy formation. This approach is validated in 16 different TMDCs. The presence of metal vacancies strongly modified their magnetic and electronic properties, correlated with the unpaired chalcogen p and metal d electrons surrounding vacancies and adjacent distortions. These findings show a generic approach for engineering interior metal atoms with atomic precision, creating opportunities to exploit quantum phenomena at the atomic scale.